EP3689454B1 - Honeycomb catalyst - Google Patents

Honeycomb catalyst Download PDF

Info

Publication number
EP3689454B1
EP3689454B1 EP18860499.5A EP18860499A EP3689454B1 EP 3689454 B1 EP3689454 B1 EP 3689454B1 EP 18860499 A EP18860499 A EP 18860499A EP 3689454 B1 EP3689454 B1 EP 3689454B1
Authority
EP
European Patent Office
Prior art keywords
honeycomb
catalytic converter
carrier layer
honeycomb catalytic
partition wall
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP18860499.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3689454A1 (en
EP3689454A4 (en
Inventor
Shinnosuke Goto
Takeru Yoshida
Takumi TOJO
Hiromasa Suzuki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ibiden Co Ltd
Toyota Motor Corp
Original Assignee
Ibiden Co Ltd
Toyota Motor Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ibiden Co Ltd, Toyota Motor Corp filed Critical Ibiden Co Ltd
Publication of EP3689454A1 publication Critical patent/EP3689454A1/en
Publication of EP3689454A4 publication Critical patent/EP3689454A4/en
Application granted granted Critical
Publication of EP3689454B1 publication Critical patent/EP3689454B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
    • B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
    • B01D53/9468—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick in different layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F01N13/0097—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are arranged in a single housing
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/101—Three-way catalysts
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2825—Ceramics
    • F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2892—Exhaust flow directors or the like, e.g. upstream of catalytic device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/902—Multilayered catalyst
    • B01D2255/9022—Two layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/905—Catalysts having a gradually changing coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/908—O2-storage component incorporated in the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9202—Linear dimensions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/20—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a flow director or deflector
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/36—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being an exhaust flap
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/02—Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a honeycomb catalytic converter.
  • Exhaust gas discharged from internal combustion engines of automobiles and the like contains harmful gases such as carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons (HC).
  • An exhaust gas catalytic converter that decomposes such harmful gases is also referred to as a three-way catalytic converter.
  • a common three-way catalytic converter includes a catalyst layer that is formed by wash-coating the slurry containing noble metal particles having catalytic activity on a honeycomb monolithic substrate made of cordierite or the like.
  • Patent Literature 1 discloses an exhaust gas catalytic converter including a Pd-carrying porous substrate and a Rh-carrying coat layer made of a ceria-zirconia solid solution on the porous substrate.
  • US 2018/229183 A1 discloses honeycomb catalyst, comprising distinct Pd and Rh containing layers.
  • Patent Literature 1 JP 2017-39069 A
  • the present inventors conducted extensive studies on the exhaust gas catalytic converter disclosed in Patent Literature 1. As a result, the present inventors found that the catalytic activity of Pd supported on the porous substrate is not sufficiently exhibited.
  • Patent Literature 1 a coat layer in which Rh having an effect to reduce NOx is supported in a solid solution of ceria and zirconia is formed on the porous substrate carrying Pd having an effect to oxidize CO and HC.
  • HC has a larger molecular size, presumably, HC does not easily diffuse from a surface of the coat layer made of a solid solution of ceria and zirconia to the porous substrate side, and cannot sufficiently reach the inside of the porous substrate where Pd is present.
  • An object of the present invention is to provide a honeycomb catalytic converter capable of achieving higher HC conversion performance.
  • the present invention provides a honeycomb catalytic converter including: a honeycomb structured body in which multiple through-holes are arranged longitudinally in parallel with one another with a partition wall therebetween; and a noble metal supported on the honeycomb structured body, wherein the honeycomb structured body contains a ceria-zirconia complex oxide and alumina, each partition wall includes a a first carrier layer defining a surface layer of the partition wall and carrying Pd, and a second carrier layer located more inwardly of the partition wall than the first carrier layer and carrying Rh.
  • Rh is supported on the second carrier layer.
  • NOx has a smaller molecular size than HC and thus easily reaches the second carrier layer.
  • Rh can sufficiently exhibit its function as a NOx reduction catalyst.
  • the Rh concentration on the first carrier layer side of the second carrier layer is higher than the Rh concentration in the center of the second carrier layer.
  • Rh concentration on the first carrier layer side of the second carrier layer is higher than the Rh concentration in the center of the second carrier layer (i.e., Rh is concentrated on the first carrier layer side), Rh can exhibit catalytic activity even when NOx does not reach the deep portion of the second carrier layer, thus easily achieving higher exhaust gas conversion performance.
  • a combination of a 10 ⁇ m ⁇ 10 um region in the center (a central portion in the thickness direction) of a second carrier layer and a 10 ⁇ m ⁇ 10 um region on a surface of the second carrier layer away from the center and located on the first carrier layer side is selected from second carrier layer portions in an element mapping image of the partition walls. Ten such combinations are randomly selected. Subsequently, in each combination of the regions, the Rh concentration is compared between the 10 ⁇ m ⁇ 10 um region in the center of the second carrier layer and the 10 ⁇ m ⁇ 10 um region on the surface of the second carrier layer.
  • the Rh concentration of the element in the 10 ⁇ m ⁇ 10 um region on the surface of the second carrier layer is higher than the Rh concentration in the 10 ⁇ m ⁇ 10 um region in the center of the second carrier layer in all the combinations, the Rh concentration of on the surface on the first carrier layer side of the second carrier layer is determined to be higher than the Rh concentration in the center of the second carrier layer.
  • the honeycomb structured body further contains an inorganic binder.
  • the mechanical strength of the honeycomb structured body can be increased.
  • the first carrier layer is a coat layer containing a ceria-zirconia complex oxide, alumina, and Pd
  • the second carrier layer is an extrudate containing ceria-zirconia complex oxide particles and alumina particles.
  • the first carrier layer is a coat layer containing a ceria-zirconia complex oxide, alumina, and Pd
  • Pd on the first carrier layer can sufficient exhibit catalytic effect (exhaust gas conversion performance).
  • the second carried layer is an extrudate, the entire honeycomb catalytic converter can be used for conversion of exhaust gas.
  • each partition wall has a thickness of 0.10 to 0.25 mm.
  • the partition walls each have a thickness in the above range, the mechanical strength and the exhaust gas conversion performance of the honeycomb catalytic converter can be easily achieved in a balanced manner.
  • the second carrier layer of each partition wall has a thickness of 0.05 to 0.20 mm.
  • the second carrier layers each have a thickness in the above range, the second carrier layers can be entirely used for conversion of exhaust gas while the strength is maintained at a high level.
  • the honeycomb catalytic converter has a length to diameter ratio (length/diameter) of 0.5 to 1.1.
  • honeycomb catalytic converter having a shape with a length to diameter ratio in the above range can easily achieve the required exhaust gas conversion performance while the pressure loss in the honeycomb catalytic converter is kept low.
  • the honeycomb catalytic converter has a diameter of 130 mm or less.
  • honeycomb catalytic converter having a diameter of 130 mm or less can be made less susceptible to breakage from thermal shock.
  • the honeycomb catalytic converter contains 25 to 75 wt% ceria-zirconia complex oxide.
  • the honeycomb catalytic converter can have a higher oxygen storage capacity (OSC).
  • honeycomb catalytic converter of the present invention is described.
  • the honeycomb catalytic converter of the present invention includes a honeycomb structured body in which multiple through-holes are arranged longitudinally in parallel with one another with a partition wall therebetween, and a noble metal supported on the honeycomb structured body.
  • the honeycomb structured body contains a ceria-zirconia complex oxide (hereinafter also referred to as "CZ ”) and alumina.
  • CZ ceria-zirconia complex oxide
  • honeycomb catalytic converter of the present invention contains the above components can be confirmed by X-ray diffraction (XRD).
  • FIG. 1 is a schematic perspective view of an example of the honeycomb catalytic converter of the present invention.
  • a honeycomb catalytic converter 10 shown in FIG. 1 includes a single honeycomb structured body 11 in which multiple through-holes 12 are arranged longitudinally in parallel with one another with a partition wall 13 therebetween.
  • the honeycomb structured body 11 contains CZ particles and alumina particles, and carries a noble metal.
  • each partition wall includes a a first carrier layer defining a surface layer of the partition wall and carrying palladium (Pd) and a second carrier layer located more inwardly of the partition wall than the first carrier layer and carrying rhodium (Rh).
  • the catalyst (Pd) that oxidizes HC that does not easily diffuse into the partition walls is present in the surface layer of each partition wall, thus achieving higher exhaust gas conversion performance.
  • FIG. 2 is a schematic cross-sectional view of an example of the partition walls constituting the honeycomb catalytic converter of the present invention.
  • each partition wall 13 includes a first carrier layer 13a defining a surface layer of the partition wall 13, and a second carrier layer 13b located more inwardly of the partition wall 13 than the first carrier layer 13a in a thickness direction of the partition wall 13 (direction indicated by a double-headed arrow t in FIG. 2 ).
  • Each first carrier layer 13a carries palladium 14a which is a noble metal
  • each second carrier layer 13b carries rhodium 14b which is a noble metal.
  • FIG. 3 is a schematic cross-sectional view of another example of partition walls constituting the honeycomb catalytic converter of the present invention. As shown in FIG. 3 , the rhodium 14b may be supported in a concentrated manner on the first carrier layer 13a side.
  • Rh When Rh is supported in a concentrated manner on the first carrier layer side, the Rh exhibits NOx conversion effect before exhaust gas reaches near the center of the partition wall. This makes it possible to increase exhaust gas conversion performance at the time of warm-up operation (which is also referred to as "warm-up performance") during which exhaust gas does not easily diffuse into the partition walls.
  • a combination of a 10 ⁇ m ⁇ 10 ⁇ m region in the center (a central portion in the thickness direction) of a second carrier layer and a 10 ⁇ m ⁇ 10 ⁇ m region on a surface of the second carrier layer away from the center and located on the first carrier layer side is selected from second carrier layer portions in an element mapping image of the partition walls. Ten such combinations are randomly selected. Subsequently, in each combination of the regions, the Rh concentration is compared between the 10 ⁇ m ⁇ 10 ⁇ m region in the center of the second carrier layer and the 10 ⁇ m ⁇ 10 ⁇ m region on the surface of the second carrier layer.
  • the Rh concentration in the 10 ⁇ m ⁇ 10 um region on the surface of the second carrier layer is higher than the Rh concentration in the 10 ⁇ m ⁇ 10 um region in the center of the second carrier layer in all the combinations
  • the Rh concentration of on the surface on the first carrier layer side of the second carrier layer is determined to be higher than the Rh concentration in the center of the second carrier layer.
  • the concentration of the noble metal can be determined from the hue and shade of the element mapping image.
  • the honeycomb structured body defining the honeycomb catalytic converter may include a single honeycomb fired body or multiple honeycomb fired bodies, and the multiple honeycomb fired bodies may be combined together with an adhesive layer.
  • the honeycomb fired body is produced by extrusion-molding a raw material paste containing ceria-zirconia composite oxide particles (hereinafter also referred to as "CZ particles") and alumina particles, and firing the resulting extrudate.
  • CZ particles ceria-zirconia composite oxide particles
  • the second carrier layer is preferably formed by supporting Rh on the honeycomb fired body obtained by firing an extrudate containing ceria-zirconia composite oxide particles and alumina particles.
  • Each partition wall constituting the honeycomb fired body may include a coat layer on a surface.
  • the first carrier layer can be formed by forming a coat layer containing Pd.
  • the first carrier layer is a coat layer containing a ceria-zirconia composite oxide, alumina, and Pd.
  • the honeycomb catalytic converter may include a peripheral coat layer on the outer periphery of the honeycomb fired body.
  • CZ particles contained in the honeycomb catalytic converter have an average particle size of 1 to 50 um.
  • the average particle size of the CZ particles is more preferably 1 to 30 um.
  • the resulting honeycomb catalytic converter has a larger surface area, thus achieving a higher OSC.
  • the alumina particles contained in the honeycomb catalytic converter may have any average particle size. Yet, in order to increase exhaust gas conversion performance, the average particle size is preferably 1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m.
  • the average particle sizes of the CZ particles and alumina particles contained in the honeycomb catalytic converter can be determined by taking a scanning electron microscope (SEM) image of the honeycomb catalytic converter with a SEM (S-4800 available from Hitachi High-Technologies Corporation).
  • SEM scanning electron microscope
  • the honeycomb catalytic converter contains 25 to 75 wt% ceria-zirconia complex oxide.
  • the honeycomb catalytic converter can achieve a higher OSC.
  • the honeycomb catalytic converter contains 15 to 35 wt% alumina particles.
  • ceria in the ceria-zirconia complex oxide of the CZ particles has an OSC.
  • the ceria-zirconia complex oxide preferably forms a solid solution of ceria and zirconia.
  • the amount of ceria in the ceria-zirconia complex oxide is preferably 30 wt% or more, more preferably 40 wt% or more, and preferably 90 wt% or less, more preferably 80 wt% or less.
  • the amount of zirconia in the ceria-zirconia complex oxide is preferably 60 wt% or less, more preferably 50 wt% or less.
  • Such a ceria-zirconia complex oxide has a high ceria content and thus has a high OSC.
  • the alumina particles may be of any type, but ⁇ -phase alumina particles (hereinafter also referred to as " ⁇ -alumina particles”) are preferred.
  • ⁇ -phase alumina particles as dividers for the ceria-zirconia complex oxide can inhibit sintering of alumina particles to one another by heat during use, allowing for sustained catalytic function. Further, use of ⁇ -phase alumina particles can increase heat resistance.
  • the honeycomb catalytic converter preferably contains inorganic particles used as an inorganic binder during the production, and more preferably contains ⁇ -alumina particles derived from boehmite.
  • the honeycomb catalytic converter preferably contains inorganic fibers, more preferably alumina fibers.
  • honeycomb catalytic converter containing inorganic fibers such as alumina fibers can have better mechanical characteristics.
  • the inorganic fibers are those having an aspect ratio of 5 or more, and the inorganic particles are those having an aspect ratio of less than 5.
  • the honeycomb catalytic converter preferably has a length to diameter ratio (length/diameter) of 0.5 to 1.1, more preferably 0.6 to 0.8.
  • the diameter of the honeycomb catalytic converter is preferably 130 mm or less, more preferably 125 mm or less.
  • the diameter of the honeycomb catalytic converter is also preferably 85 mm or more.
  • the length of the honeycomb catalytic converter is preferably 65 to 120 mm, more preferably 70 to 110 mm.
  • the shape of the honeycomb catalytic converter is not limited to a round pillar shape.
  • Examples include a prism, a cylindroid shape, a pillar shape having an end face with a racetrack shape, and a prism with rounded corners (e.g., a triangular pillar shape with rounded corners).
  • each partition wall of the honeycomb catalytic converter has the same thickness.
  • the thickness of each partition wall of the honeycomb catalytic converter is preferably 0.10 to 0.25 mm, more preferably 0.10 to 0.15 mm.
  • the thickness of the first carrier layer on one side of each partition wall is preferably 0.01 to 0.10 mm, more preferably 0.02 to 0.05 mm.
  • the thickness of the second carrier layer on one side of each partition wall is preferably 0.05 to 0.20 mm, more preferably 0.05 to 0.15 mm.
  • the shape of the through-holes is not limited to a quadrangular pillar shape.
  • it may be a triangular pillar shape or a hexagonal pillar shape.
  • the density of the through-holes in a cross section perpendicular to the longitudinal direction of the honeycomb catalytic converter is 31 to 155 pcs/cm 2 .
  • the honeycomb catalytic converter has a porosity of 40 to 70%.
  • the porosity of the honeycomb catalytic converter is in the above range, the honeycomb catalytic converter can exhibit high exhaust gas conversion performance while the strength is maintained.
  • the porosity of the honeycomb catalytic converter can be measured by a weighing method described below.
  • the honeycomb catalytic converter may include a peripheral coat layer on the outer periphery of the honeycomb fired body.
  • the thickness of the peripheral coat layer is preferably 0.1 to 2.0 mm.
  • honeycomb catalytic converter of the present invention noble metals are supported on the honeycomb structured body.
  • noble metals examples include Pd supported on the first carrier layers and Rh supported on the second carrier layers.
  • Rh When supporting Rh on the second carrier layer, if it is desired that Rh is supported in a concentrated manner on the surface side of each second carrier layer (i.e., the surface on which the first carrier layer is to be formed in the later step), Rh may be supported by a method that includes impregnating the honeycomb fired body with a rhodium nitrate solution, for example.
  • the total amount of the noble metals supported is preferably 0.1 to 15 g/L, more preferably 0.5 to 10 g/L.
  • amount of the noble metals supported refers to the weight of the noble metals per apparent volume of the honeycomb catalytic converter.
  • the apparent volume of the honeycomb catalytic converter includes the volume of pores and cells, and it includes the volume of the peripheral coat layer and/or the volume of an adhesive layer.
  • the method of producing the honeycomb catalytic converter of the present invention may be, for example, a method that includes a supporting step of supporting Rh on a honeycomb fired body produced by the method described below, and a coat layer forming step of forming a coat layer containing Pd, CZ raw materials, and alumina particles on a surface of each partition wall.
  • the method of producing a honeycomb fired body may be, for example, a method that includes a molding step of molding a raw material paste containing CZ particles and alumina particles into a honeycomb molded body in which multiple through-holes are arranged longitudinally in parallel with one another with a partition wall therebetween, and a firing step of firing the honeycomb molded body to produce a honeycomb fired body.
  • a raw material paste containing CZ particles and alumina particles is prepared.
  • the average particle sizes of the CZ particles and the alumina particles used as raw materials of the honeycomb catalytic converter can be determined by a laser diffraction particle size distribution meter (Mastersizer 2000 available from Malvern Panalytical).
  • Examples of other raw materials used to prepare the raw material paste include inorganic fibers, inorganic binders, organic binders, forming auxiliaries, and dispersion media.
  • the inorganic fibers may be made of any material. Examples include alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, and aluminum borate. Two or more of these may be used in combination. Of these, alumina fibers are preferred.
  • the inorganic fibers preferably have an aspect ratio of 5 to 300, more preferably 10 to 200, still more preferably 10 to 100.
  • any inorganic binder may be used.
  • examples include solids contained in materials such as alumina sol, silica sol, titania sol, sodium silicate, sepiolite, attapulgite, and boehmite. Two or more of these inorganic binders may be used in combination.
  • Boehmite is alumina monohydrate with a composition of AlOOH, and has good dispersibility in media such as water. Thus, boehmite is preferably used as an inorganic binder.
  • Any organic binder may be used. Examples include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, polyethylene glycol, phenolic resin, and epoxy resin. Two or more of these may be used in combination.
  • Any pore-forming agent may be used.
  • examples include acrylic resins, coke, and starch.
  • use of two or more selected from acrylic resins, coke, and starch is preferred.
  • the pore-forming agent is one that is used to introduce pores into a honeycomb fired body when producing a honeycomb fired body.
  • Any forming auxiliary may be used. Examples include ethylene glycol, dextrins, fatty acids, fatty acid soaps, and polyalcohols. Two or more of these may be used in combination.
  • Any dispersion medium may be used. Examples include water, organic solvents such as benzene, and alcohols such as methanol. Two or more of these may be used in combination.
  • the proportions of these materials relative to the total solids remaining in the raw material paste after the firing step are preferably as follows: CZ particles: 25 to 75 wt%; alumina particles: 15 to 35 wt%; alumina fibers: 5 to 15 wt%, and boehmite: 5 to 20 wt%.
  • Preparation of the raw material paste preferably involves mixing/kneading of the raw materials.
  • a device such as a mixer or an attritor may be used for mixing, or a device such as a kneader may be used for kneading.
  • the raw material paste is molded into a honeycomb molded body in which multiple through-holes are arranged longitudinally in parallel with one another with a partition wall therebetween.
  • the raw material paste is extrusion-molded into a honeycomb molded body. More specifically, the raw material paste is passed through a die of a specific shape to form a continuous honeycomb molded body having through-holes of a specific shape, and the continuous honeycomb molded body is cut to a specific length, whereby a honeycomb molded body is obtained.
  • a dryer such as a microwave dryer, a hot-air dryer, a dielectric dryer, a reduced-pressure dryer, a vacuum dryer, or a freeze-dryer is used to dry the honeycomb molded body to produce a honeycomb dried body.
  • honeycomb molded body and the honeycomb dried body before the firing step are also collectively referred to as a "honeycomb molded body".
  • the honeycomb molded body is fired to produce a honeycomb fired body.
  • the honeycomb molded body is degreased and fired.
  • the step can also be referred to as a "degreasing/firing step”, but is referred to as a “firing step” for the purpose of convenience.
  • the temperature in the firing step is preferably 800°C to 1300°C, more preferably 900°C to 1200°C.
  • the duration of the firing step is preferably 1 to 24 hours, more preferably 3 to 18 hours.
  • the atmosphere of the firing step is not limited, but an atmosphere with an oxygen concentration of 1 to 20% is preferred.
  • the honeycomb fired body can be produced by the above steps.
  • Rh is supported on the honeycomb fired body to form a second carrier layer.
  • Rh is supported on the partition walls by a method that includes immersing the honeycomb fired body in a Rh-containing solution, removing the honeycomb fired body from the solution, and heating or drying the honeycomb structured body.
  • the Rh-containing solution may be, for example, a dispersion of Rh particles or a solution of rhodium nitrate.
  • Rh is preferentially supported on the surface of each partition wall of the honeycomb fired body so that the Rh concentration on the first carrier layer side of the second carrier layer is higher than the Rh concentration in the center of the second carrier layer.
  • Rh is preferentially supported on the surface of each partition wall by a method that includes immersing the honeycomb fired body in a Rh-containing solution which is easily adsorbed onto the surface of the partition wall, removing the honeycomb fired body from the solution, and heating or drying the honeycomb structured body.
  • Example of the Rh-containing solution which is easily adsorbed onto the surface of each partition wall of the honey fired body includes a solution containing a Rh complex.
  • the pH of the above solution is adjusted 1.5 to 5.0 to facilitate adsorption of Rh onto the surface of the partition wall.
  • the pH of the solution can be adjusted by adding a pH adjuster.
  • the pH adjuster is preferably free of halogens such as fluorine, chlorine, and bromine, and sulfur. Examples include nitric acid and oxalic acid.
  • a slurry for forming a coat layer which is a raw material of the coat layer, is prepared.
  • the slurry for forming a coat layer is obtained by mixing CZ particles, alumina particles, and a Pd-containing material with a solvent.
  • the Pd-containing material may be a dispersion of Pd particles or a solution of a Pd complex or a Pd-containing salt.
  • CZ particles, alumina particles, a Pd-containing material, and a solvent are mixed together at once.
  • CZ particles and a Pd-containing material are first mixed together to obtain Pd-carrying CZ particles, and subsequently, the Pd-carrying CZ particles, alumina particles, and a solvent are mixed together.
  • alumina particles and a Pd-containing material are first mixed together to obtain a Pd-carrying alumina particles, and subsequently, the Pd-carrying alumina particles, CZ particles, and a solvent are mixed together.
  • Examples of other raw materials used to prepare the slurry for forming a coat layer include inorganic binders and dispersion media.
  • Such other raw materials are preferably those used in the raw material paste to produce a honeycomb molded body.
  • honeycomb fired body in which Rh is supported on the partition walls is immersed in the slurry for forming a coat layer, and removed from the slurry, followed by drying and firing, whereby the honeycomb catalytic converter of the present invention can be obtained in which the coat layer containing Pd is formed on the surface of each partition wall constituting the honeycomb fired body carrying Rh.
  • the total amount of the noble metals supported in the coat layer forming step is preferably adjusted to 0.1 to 15 g/L, more preferably 0.5 to 10 g/L.
  • the peripheral coat layer can be formed by applying a peripheral coat layer paste to the outer periphery of the honeycomb fired body excluding both end faces thereof, and then solidifying the peripheral coat layer paste by drying.
  • the peripheral coat layer paste may have the same composition as that of the raw material paste.
  • the step of forming a peripheral coat layer is performed after the coat layer forming step.
  • the honeycomb structured body When a honeycomb structured body in which multiple honeycomb fired bodies are combined together with an adhesive layer therebetween is used, the honeycomb structured body can be produced by applying an adhesive layer paste to the outer periphery of each honeycomb fired body excluding both end faces thereof, combining the honeycomb fired bodies, and solidifying the adhesive layer paste by drying.
  • the adhesive layer paste may have the same composition as that of the raw material paste.
  • the raw material paste was extrusion-molded into a round pillar-shaped honeycomb molded body. Then, using a reduced-pressure microwave dryer, the honeycomb molded body was dried at an output of 1.74 kW under a reduced pressure of 6.7 kPa for 12 minutes, and then degreased/fired at 1100°C for 10 hours, whereby a honeycomb fired body was produced.
  • the honeycomb fired body had a round pillar shape with a diameter of 103 mm and a length of 105 mm in which the density of the through-holes was 77.5 pcs/cm 2 (500 cpsi) and the thickness of each partition wall was 0.076 mm (3 mil).
  • the honeycomb fired body was immersed and kept in a rhodium nitrate solution (Rh(NO 3 ) 3 , Rh concentration: 30 g/L) for 24 hours. Subsequently, the honeycomb fired body was removed from the rhodium nitrate solution, dried at 110°C for 2 hours, and fired at 500°C for 1 hour in a nitrogen atmosphere, whereby Rh was supported on the surface of each partition wall constituting the honeycomb fired body.
  • Rh(NO 3 ) 3 Rh concentration: 30 g/L
  • the amount of Rh supported was 0.4 g/L per apparent volume of the honeycomb fired body.
  • the Rh-carrying honeycomb fired body was immersed in the slurry for forming a coat layer. Then, the honeycomb fired body was removed from the slurry for forming a coat layer, and excess slurry attached to the honeycomb fired body was blown off by a blower. Subsequently, the honeycomb fired body was dried at 80°C for 24 hours, and fired at 500°C for 1 hour, whereby a honeycomb catalytic converter according to Example 1 in which a coat layer containing a Pd was formed on the surface of each partition wall was obtained.
  • the amount of Pd supported was 1.2 g/L per apparent volume of the honeycomb catalytic converter.
  • a honeycomb catalytic converter according to Comparative Example 1 was obtained as in Example 1, except that the solution used in the supporting step was changed to a palladium nitrate solution (Pd concentration: 100 g/L) and that palladium nitrate used to produce the slurry for forming a coat layer was changed to rhodium nitrate whose amount was one-third of the amount of the rhodium nitrate.
  • a palladium nitrate solution Pd concentration: 100 g/L
  • palladium nitrate used to produce the slurry for forming a coat layer was changed to rhodium nitrate whose amount was one-third of the amount of the rhodium nitrate.
  • the amount of the noble metals, in terms of total amount of Pd and Rh, supported on the honeycomb catalytic converter according to Comparative Example 1 was 1.6 g/L per apparent volume of the honeycomb fired body.
  • Each of the honeycomb catalytic converters according to Example 1 and Comparative Example 1 was set in a V6-3.5L engine, and the temperature when the HC concentration ((HC inflow - HC outflow)/(HC inflow) ⁇ 100) was 50% or lower from the start of the stoichiometric engine was measured to evaluate the HC conversion performance.
  • Table 1 shows the results.
  • the results in Table 1 show that the temperature at which the HC concentration is 50% or lower is lower in the honeycomb catalytic converter according to Example 1 than that in the honeycomb catalytic converter according to Comparative Example 1. Thus, the honeycomb catalytic converter according to Example 1 has excellent HC conversion performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Ceramic Engineering (AREA)
  • Catalysts (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
EP18860499.5A 2017-09-27 2018-09-27 Honeycomb catalyst Active EP3689454B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017186474A JP6698602B2 (ja) 2017-09-27 2017-09-27 排ガス浄化用ハニカム触媒
PCT/JP2018/035844 WO2019065802A1 (ja) 2017-09-27 2018-09-27 ハニカム触媒

Publications (3)

Publication Number Publication Date
EP3689454A1 EP3689454A1 (en) 2020-08-05
EP3689454A4 EP3689454A4 (en) 2021-06-09
EP3689454B1 true EP3689454B1 (en) 2023-11-08

Family

ID=65901489

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18860499.5A Active EP3689454B1 (en) 2017-09-27 2018-09-27 Honeycomb catalyst

Country Status (5)

Country Link
US (1) US11298686B2 (zh)
EP (1) EP3689454B1 (zh)
JP (1) JP6698602B2 (zh)
CN (1) CN111132758B (zh)
WO (1) WO2019065802A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019058876A (ja) 2017-09-27 2019-04-18 イビデン株式会社 ハニカム触媒
JP6771005B2 (ja) * 2018-09-12 2020-10-21 イビデン株式会社 ハニカム構造体の製造方法
JP6764451B2 (ja) * 2018-09-12 2020-09-30 イビデン株式会社 ハニカム構造体の製造方法
JP7372052B2 (ja) * 2019-05-15 2023-10-31 株式会社キャタラー 排ガス浄化触媒装置
JP2024522426A (ja) * 2021-06-10 2024-06-21 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 錯化剤及び還元剤としてタンニン酸を使用するパラジウム固定及び低い未使用酸素吸蔵能
JP2024525265A (ja) * 2021-06-10 2024-07-12 ジョンソン、マッセイ、パブリック、リミテッド、カンパニー 錯化剤及び還元剤としてロジウム／白金及びタンニン酸を使用する改善されたｔｗｃ活性

Family Cites Families (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6268543A (ja) 1985-09-21 1987-03-28 Toyota Motor Corp 排気ガス浄化用モノリス触媒
US5139992A (en) 1989-11-08 1992-08-18 Engelhard Corporation Three-way conversion catalyst including a ceria-containing zirconia support
US5296198A (en) * 1990-11-09 1994-03-22 Ngk Insulators, Ltd. Heater and catalytic converter
DE69130894T2 (de) 1990-11-26 1999-09-02 Tanaka Kikinzoku Kogyo K.K. Palladium katalysatoren für unvollständige verbrennung und verfahren zu deren verwendung
JP2848970B2 (ja) * 1990-12-21 1999-01-20 日本碍子株式会社 ハニカムヒーター及び触媒コンバーター
US5376610A (en) * 1992-04-15 1994-12-27 Nissan Motor Co., Ltd. Catalyst for exhaust gas purification and method for exhaust gas purification
JP3281087B2 (ja) * 1993-02-10 2002-05-13 日本碍子株式会社 排ガス浄化用触媒
JPH0760117A (ja) 1993-08-30 1995-03-07 Honda Motor Co Ltd 排気ガス浄化用触媒
US6497851B1 (en) 1994-12-06 2002-12-24 Englehard Corporation Engine exhaust treatment apparatus and method of use
JPH09262484A (ja) 1996-03-29 1997-10-07 Ngk Insulators Ltd 高耐熱衝撃性セラミックハニカム触媒
US6087298A (en) 1996-05-14 2000-07-11 Engelhard Corporation Exhaust gas treatment system
JPH09299811A (ja) 1996-05-17 1997-11-25 Ngk Insulators Ltd ハニカム構造体
JPH10296085A (ja) 1997-04-30 1998-11-10 Cataler Kogyo Kk 排ガス浄化用触媒
US6492297B1 (en) 2000-09-15 2002-12-10 Engelhard Corporation Catalyst composition for purifying exhaust gas
JP3827143B2 (ja) 2001-01-17 2006-09-27 トヨタ自動車株式会社 排ガス浄化用触媒
US20040001781A1 (en) 2002-06-27 2004-01-01 Engelhard Corporation Multi-zone catalytic converter
JP4079717B2 (ja) 2002-08-05 2008-04-23 株式会社日本自動車部品総合研究所 セラミック触媒体
JP2006075724A (ja) 2004-09-09 2006-03-23 Toyota Motor Corp 排ガス浄化用触媒
EP1795262B1 (en) * 2004-09-30 2010-01-27 Ibiden Co., Ltd. Honeycomb structure
WO2006057067A1 (ja) 2004-11-25 2006-06-01 Cataler Corporation 排ガス浄化用触媒
JP2006188404A (ja) 2005-01-07 2006-07-20 Denso Corp セラミックスモノリス担体及びその製造方法
JP2006205050A (ja) 2005-01-27 2006-08-10 Toyota Motor Corp 排ガス浄化用触媒
JP4669322B2 (ja) 2005-05-24 2011-04-13 株式会社キャタラー 排ガス浄化用触媒
WO2008000449A2 (de) * 2006-06-29 2008-01-03 Umicore Ag & Co. Kg Dreiweg-katalysator
JP2008023501A (ja) * 2006-07-25 2008-02-07 Toyota Motor Corp 排ガス浄化用触媒
CN100998941B (zh) 2007-01-04 2012-09-05 华东理工大学 一种前置催化剂及其制备方法
US8636959B2 (en) * 2007-05-09 2014-01-28 N.E. Chemcat Corporation Selective catalytic reduction type catalyst, and exhaust gas purification equipment and purifying process of exhaust gas using the same
JP5173282B2 (ja) 2007-07-04 2013-04-03 株式会社キャタラー 排ガス浄化用触媒
US7871452B2 (en) * 2007-10-01 2011-01-18 Mazda Motor Corporation Particulate filter
WO2009118815A1 (ja) * 2008-03-24 2009-10-01 イビデン株式会社 ハニカム構造体
WO2009118866A1 (ja) * 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体
WO2009118867A1 (ja) 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体および排ガス処理装置
JP2009255032A (ja) * 2008-03-27 2009-11-05 Ibiden Co Ltd ハニカム構造体
WO2009118869A1 (ja) 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体および排ガス処理装置
WO2009118872A1 (ja) * 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体
WO2009118871A1 (ja) * 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体
WO2009118868A1 (ja) * 2008-03-27 2009-10-01 イビデン株式会社 ハニカム構造体
JP2009273988A (ja) 2008-05-13 2009-11-26 Toyota Motor Corp 排ガス浄化用触媒
WO2009141893A1 (ja) * 2008-05-20 2009-11-26 イビデン株式会社 ハニカム構造体
WO2009141891A1 (ja) 2008-05-20 2009-11-26 イビデン株式会社 ハニカム構造体
JP5322526B2 (ja) * 2008-07-17 2013-10-23 エヌ・イーケムキャット株式会社 自動車から排出される排気ガスを浄化するためのハニカム構造型触媒及びその製造方法、並びに、その触媒を使用した排気ガス浄化方法
JP2010127210A (ja) 2008-11-28 2010-06-10 Toyota Motor Corp 排ガス浄化方法
CN102665910B (zh) * 2009-11-19 2014-07-02 揖斐电株式会社 蜂窝结构体以及尾气净化装置
JP5903205B2 (ja) * 2010-01-04 2016-04-13 株式会社キャタラー 排ガス浄化用触媒
US9120056B2 (en) 2010-02-16 2015-09-01 Ford Global Technologies, Llc Catalyst assembly for treating engine exhaust
FR2957529B1 (fr) * 2010-03-19 2012-04-06 Saint Gobain Ct Recherches Structure filtrante comprenant un materiau de bouchage ameliore
EP2556871B1 (en) 2010-03-31 2016-09-07 NGK Insulators, Ltd. Honeycomb filter
JP5573710B2 (ja) 2010-07-23 2014-08-20 トヨタ自動車株式会社 排ガス浄化用触媒
JP5376261B2 (ja) * 2011-03-10 2013-12-25 トヨタ自動車株式会社 排ガス浄化用触媒
JPWO2012137930A1 (ja) * 2011-04-08 2014-07-28 トヨタ自動車株式会社 排ガス浄化用酸化触媒
PL2861533T3 (pl) 2012-06-15 2020-07-13 Basf Corporation Kompozyty mieszanych tlenków metali do magazynowania tlenu
EP2877266B1 (en) * 2012-07-26 2016-06-29 Cormetech, Inc. Honeycomb catalytic assemblies and applications thereof
GB201220912D0 (en) 2012-11-21 2013-01-02 Johnson Matthey Plc Oxidation catalyst for treating the exhaust gas of a compression ignition engine
US9266092B2 (en) 2013-01-24 2016-02-23 Basf Corporation Automotive catalyst composites having a two-metal layer
JP6204023B2 (ja) 2013-01-31 2017-09-27 株式会社キャタラー 排ガス浄化用触媒
JP5846137B2 (ja) 2013-02-13 2016-01-20 トヨタ自動車株式会社 触媒コンバーター
JP6208540B2 (ja) 2013-10-29 2017-10-04 トヨタ自動車株式会社 排ガス浄化触媒
JP6471098B2 (ja) 2013-12-11 2019-02-13 株式会社キャタラー 排ガス浄化用触媒
JP6219796B2 (ja) * 2014-09-04 2017-10-25 日本碍子株式会社 ハニカムフィルタ
JP6350142B2 (ja) * 2014-09-08 2018-07-04 株式会社デンソー ハニカム構造体及びその製造方法
US10232299B2 (en) * 2014-09-11 2019-03-19 Ngk Insulators, Ltd. Honeycomb structure
EP3207989B2 (en) 2014-10-16 2023-07-19 Cataler Corporation Exhaust gas purification catalyst
JP6565184B2 (ja) 2014-12-26 2019-08-28 日産自動車株式会社 ハニカム型モノリス触媒およびその製造方法
JP6545962B2 (ja) 2015-01-22 2019-07-17 株式会社キャタラー 排ガス浄化用触媒
JP6354670B2 (ja) * 2015-06-08 2018-07-11 株式会社デンソー ハニカム構造体及びその製造方法
JP6540260B2 (ja) * 2015-06-18 2019-07-10 株式会社デンソー ハニカム構造体及び自動車用触媒コンバータ
JP6572675B2 (ja) * 2015-08-18 2019-09-11 株式会社デンソー 排ガス浄化触媒
GB201518784D0 (en) 2015-10-23 2015-12-09 Johnson Matthey Plc Catalysed monolith substrate for a diesel engine
WO2017213105A1 (ja) * 2016-06-07 2017-12-14 株式会社キャタラー 排ガス浄化用触媒
WO2018012562A1 (ja) * 2016-07-14 2018-01-18 イビデン株式会社 ハニカム構造体及び該ハニカム構造体の製造方法
CN109414689A (zh) * 2016-07-14 2019-03-01 揖斐电株式会社 蜂窝结构体和该蜂窝结构体的制造方法
CN109414690A (zh) * 2016-07-14 2019-03-01 揖斐电株式会社 蜂窝结构体和该蜂窝结构体的制造方法

Also Published As

Publication number Publication date
WO2019065802A1 (ja) 2019-04-04
US11298686B2 (en) 2022-04-12
US20200222883A1 (en) 2020-07-16
CN111132758B (zh) 2023-04-07
JP2019058873A (ja) 2019-04-18
EP3689454A1 (en) 2020-08-05
CN111132758A (zh) 2020-05-08
EP3689454A4 (en) 2021-06-09
JP6698602B2 (ja) 2020-05-27

Similar Documents

Publication Publication Date Title
EP3689454B1 (en) Honeycomb catalyst
US11298687B2 (en) Honeycomb catalytic converter
JP6998871B2 (ja) ハニカム構造体及び該ハニカム構造体の製造方法
US20200222889A1 (en) Honeycomb catalytic converter
US11298685B2 (en) Honeycomb catalytic converter
US20200222890A1 (en) Honeycomb catalytic converter
US11618009B2 (en) Honeycomb catalytic converter
WO2019065797A1 (ja) ハニカム触媒
JP6949019B2 (ja) ハニカム構造体及び該ハニカム構造体の製造方法
JP6845777B2 (ja) ハニカム触媒の製造方法
WO2019026645A1 (ja) ハニカム構造体の製造方法及びハニカム構造体
JP6944833B2 (ja) ハニカム構造体の製造方法
WO2020105666A1 (ja) ハニカム構造体
JP2019155277A (ja) ハニカムフィルタ

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200326

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20210511

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 23/63 20060101AFI20210505BHEP

Ipc: B01D 53/94 20060101ALI20210505BHEP

Ipc: B01J 35/04 20060101ALI20210505BHEP

Ipc: F01N 3/10 20060101ALI20210505BHEP

Ipc: F01N 3/28 20060101ALI20210505BHEP

Ipc: B01J 23/44 20060101ALI20210505BHEP

Ipc: B01J 23/46 20060101ALI20210505BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20230609

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230913

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 602018060959

Country of ref document: DE

Owner name: TOYOTA JIDOSHA KABUSHIKI KAISHA, TOYOTA-SHI, JP

Free format text: FORMER OWNER: IBIDEN CO., LTD., OGAKI-SHI, GIFU, JP

Ref country code: DE

Ref legal event code: R081

Ref document number: 602018060959

Country of ref document: DE

Owner name: IBIDEN CO., LTD., OGAKI-SHI, JP

Free format text: FORMER OWNER: IBIDEN CO., LTD., OGAKI-SHI, GIFU, JP

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602018060959

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1629146

Country of ref document: AT

Kind code of ref document: T

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240308

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240209

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240208

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20240208

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20231108

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602018060959

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240730

Year of fee payment: 7

26N No opposition filed

Effective date: 20240809